Method of providing a new product



Patented Nov. 21,1944 a f ivmrnon 0F PROYIDINQA New septum 1 i Jacqueline. :Halrv'ey, Jr., Washington; D1 or, an

Harveyr: J12, andone-half to-SouthernUWoo t:

Eastjioint; Gar, acorpo Preserving Company,

ration. of Geor i No nrawingi ApplicationDecember-zl; V 'SerialNMA69fl23" t S CI aims. (01. lee-45o) I a The instant" invention relates to" the produc sectieidesa nd m @113" other service; to whi h toxicoils may beut a 1 p l 2 a l Moreespecially the instantinventionflrelates to the: production of' toxic oils from mixtures of gravities falling within the hereinafter petroleum fractions characterized by ring struc? i ture content. Among, such starting materials maybe mentioned miXturesQ of petroleum tractionsccharacterized by ringstructurecontent recovered" from petroleum fractions by well known extraction methods including extractive .distil lation and? azeotropic. distillation. Also ,may be mentioneqi ure Q e roleum t than acteriz edfl by ring, structure" content as flowing from thermal andjorf catalytic ltreatment ofl 1 certain petroleumfractions which includesjpei troleum fractions having ring structures induced in the course of thermal' and/or catalytic treat -j 3 ment, as for-example having ring structuresim duced in the course of one or more thermal and/or'catalytic treatments of unusual length,

asfor example forperiodsof from 1 19: hours or m oreg i t it v 1 obj'ect ot the instant invention" is thepro duction of toxic oils from the aforenamed petroleum fractions? orpthers whereby to provide oils, ofithe preservativefltype as for example preservative woo cl impregnants conforming to l pqcificationsextantpor acceptabletotthe trade consuming such. oil; materials.

Another object of the instant provision of preservative wood impregnants hav ing boiling'ranges and residuesin accordance with published speeificationsand/or in accordance with, consumer! preference.

;Another object of the instant invention is thel reforming, modifying, converting and/ or trans: forming-of the mixtures of hydrocarbons where'- 1 bv to induce tokicityr Another: object of theinstantinvention is the unveiling ofiflatent toxicity in-mixtures ofpetroieum' fractions having inherent but inhibited toxicity.

Another; object of the instant invention same coordination 0t process variables so as to providespeeificgravitieswithin-definite limits in various fractions of the beneficiated:material. p Another objectof th e instant invention is a coordinationiof :process variables whichtwill prov videl in; various fractional parts for the! bene- Another object of the instant invention is the. induction of toxicity in the presence: :of a relformingcatalyst adaptedto favorablylinfluencethe inductiom of toxicity: By the expression, la

reforming catalyst? is meant a catalytic-mater:

rialadapted' to favorably-exertacatalytic; infill?" ence whilst the startings material is; beingyyl'eformed, transformed, modifiedtand/or: converted in accordance with the instant: process whereby to induce; toxicity; In .the; specification and in v thei annexed'iclaimsreformation, transtormae tion, conversion and/or modificationh of the starting jmate'rial whereby to: induce" toxicity are specifically: mearitwto include cracking, addition, substitution and/ or subtraction reactions that are possible within thewlimits of the process variables disclosedelsewhere herein. l h i Incthe pastwood preservative oils of I the high temperature coal: tar deriveditype have been employed-in quantities greatly exceeding" the total of all other wood preservativetoils From thei standpoint of availability of said coal ,tar.

as the parent product ofwood preservative oils,; it is annually producedin this country under normal conditions to the extentgof,;.fivehundred m-illion to six hundredj million gallons: This invention 'is the quantity of coal tar is capable of yielding an amountof highly efiective wood preservative oils which would make 'this country self sufiicient in its t Wood preservative requirements, ;However,,

dueqto thefa'ct' thatwhen aflwood ipreslervative distillate (creosote) isjrecoveredffrom coal h; tar

there remainsin the still a residue (pitchl which, at"b'est, isa low pricedfproduct and.

which, at worst; is a seriously distress product to..the"end that'attimes it is placed in inventory ratherthan sold, thecurrent mfitliod'of procI-L essing 'coal'tarleaves much to be;desiredm The net result of this situation obtainingisYthat the 1 coal tar distiller usually jconfines himself to that distillation recovery of creosote-l which would ficiated material cyclie structures withwspeciflc corresp'ondto the attendingvlaniount of pitch that he can market at a profit. Accordingly, over a period of {years severalhundrednnillion gallons of creosote oil have been importedjinto this country. That such a situation should obtain is apparently a paradox inthatwe-annually produceaquantity, of high temperature :coalgtar which if processed to yieldfcreosot'e would make us self-sufficientin that requirement Asurvey or this paradox isuiully outlined in an address produced by the petroleum industry, and the high boiling oils of aromatic content produced by this industry have for several years been tested for their wood preservative efficiency.

By the term petroleum aromatic as used herein and in the appended claims is meant to include mixtures of petroleum fractions characterized by cycliccontent and include specifically various forms and types of naphthenes found in various mixtures of petroleum fractions, as for example monoc'yclic and polycyclic naphthenes.

The so-called petroleum aromatics which include the monoc'y-clic and polycyclic naphthenes and unsaturated hydrocarbon fractions have in the past been produced in very large quantities. However,very little work has been done on these materials. Such a fact is borne out on page 667, Reactions of pure hydrocarbons Gustav Egloff, Reinhold Publishing Corporation, 330 West42nd Street, New- York city, which states:

Despite the fact that naphthenes .or cycloparaflines are available in enormous quantities, as shown by an estimate of 100,000,000 barrels present in the 1,498,000,000 barrels of crude oil which was the worlds production in 1934, comparatively little work of a pyrolytic nature has may be mentioned a high boiling oil of cyclic content produced (1940) at the Wood River Refinery of the Shell Oil Company and which has the following inspection: I

1 Maximum. 'In the foregoing tabular data P. M. (1.0. means Pensky- Martin Closed Cup; C. 0. C. means Cleveland Open Cup.

Upon evaluating the foregoing oil for its toxicity to wooddestroying fungi (Madison 517), it

was found that this oil did not inhibit the growth of the fungi named at a concentration of up to and including.10%.

It is now discovered that the oil above named or other oils of cyclic content produced by the petroleum industry can be increased in toxicity in accordancewith the process of the instant invention.

According tothe instant invention oils of cyclic content produced by the petroleum industry are reformed, transformed, modified and/or converted to oils of a more toxic nature having characteristics acceptable to consumers of wood preservative impregnant and/or conforming to :wood preservative specifications extant.

Wehave discovered that the relatively nontoxic petroleum oils of cyclic content mentioned in the foregoing, or others, contain toxicity diluents which inhibit an inherently toxicmolecular structure.

We have further discovered that by thermally and /or catalytically treating these said petroleum oils of inhibited toxicity in the presence of certain substances, as for example certain oils and/ or gas or gases, we are able to transfer the toxicity diluents from the former to the latter, and thus w veil the latent toxicity in the former.

The following examples will serve to illustrate several modes of practicingthe present invention.

' Example 1.A liquid sulfur dioxide extract of matic extract and two parts of benzene.

Gravity; 10.8 Flash, P. M. c. c. F 295 Flash, C. O. C F 290 Fixed carbon per cent" 4.9 Four point F 10 B. S. & W per cent by volume 0.1 S. U. vis, 100 F l 151 S. U, vis. 210 F 41 'S. F. vis. '77 F 34.5 Carbon residue: 6.8 Per cent aromatics and unsaturatea; 82.4 S01. in CS2 99.8 Loss 50 grams,'5 hours 325 F 8.9 Residue of 100 pene per cent 37.5 A. S. T. M. distillation: l

LE, P F 518 10% rec. F 565 20% rec. F .539 30% rec. F 614 40% rec. F 637 50% rec. F 660 60% rec. F 1 6'75 The comminglement is heated in the presence of anactivated clay catalyst at a temperature of 460 C. whilst under a pressure of 1,000 pounds forsuch a length of time as to jointly provide (1) transference of toxicity diluents fromtlie molecular structure of the aromatic extract to the ben zone, (2) newly formed low boiling materials due to the orackingof the extract, as for example newly formed materials boiling at or below 235? C., and (3) an overall specific gravity in fractional parts of the beneficiated oil extract falling between the limits noted in the following tabular da a:

Fractions Low limit High limit 0. 850 l. 0315 0. 914 l. 0691 0. 973 l. 1175 and preferably between the limits noted below:

Fractions Low limit High limit to the cracking of the -extrac't and "(3) 1 a specific gravity r in fractional parts of- ""the': beneficiation falling betweem the preferred stated-limits? I Aththe end-*ofthe-stated-perid=of processing '5 I the oil is withdrawnfl'om its -itreating -enclosure,

cooled and inspected." Theunreacted benzenepit any; and the" benzene-containing at leastaiportiorr of the; former "toxicity diluents --of the aromatic extract are rernoved; partiallyorsubsumtially totallyfrom the-overall beneficiatiorr inany as for examplebydistillation 1 suitable manner,

After the total 'zenes;-t'he beneficiated aromatic-extract-is found tohave enhance'd toxic propertieSas-jointly flow= l ingfrom among other-thingsftheformationiof newly created-lovvboiling materials boiling atior below-2-35 C. andtlie-transferencefofthe toxicity diluents to the benzene;

After the partialbr total removal of 'saidbem 'zenes fromthebeneficiated extract-which hias substantial residual matter above- 355? (3., the beneficiated extract may, be used in entirety as, a preservative WOOd impregnant having commercialtozticityf, or appreservative woodiimpre'gnant -may be segregated therefrom inany well known 3. American Wood Breservers Association.

cmUpito235? C., not more-than 1 /2:%.; btUpto300 C.; not more than,16 /z 0. Up to 355".C,, not1es3tthan45.% n l American WoodPreservers Association a. Up to 210 0., not more"than-8:% b. Up 1301235": C.,, not morezthanv35f7dij American Wood-Breservers Associatiom a. Upto' 2l 0? C.,not moreatha-nrl0 b; Up to:235"C., not moreithan'r wflz i a; American WoodRreservers Association: v

n a; Up to 2102: (3., not morefthan 5%- e 7), Up to 235" (1.,not morethan i .PrussianRy. r i e l i a; Unto-150$ 0., not more than 3%? i b.. Upito L200? (3:, notmorethan 119% 0-. Up to 235 :C.,; not more than .25 NationalBaint Varnish & Lacquer Association ii-220i l l l v a. 5%.at162' C. b, 97%at27090, l v Southern pine shingle .-stain-oilj a. 51%at 1373 CM i it b. 95 at 257? C. Nevilleshingle-stain oily it i a. I. B. 33., 150- C. b. 5% at 205 C. c; 95%qat 292. C.

carbolmeumn i flnng; Moe-0W1; B. B. l

r ses-ma "tionsbcil-ing atleast as low as about zss cz due modificaticns of a existing specifications; or other or partial-removaP-o f said *bements from the starting material.

the" beneficiated'" extractnoted in the foregoing arecritical within limits Unless the lower limit is approximated toxicity unveiling will be sacri need. If an atternptis made to exceed the upper limit; as for example thepreferred--upper limit;

unwantedureactions occur. The induction and/or provision ,ofthe noted specific gravities in fractional parts of the b'enefi'ci'ated 'extract, and more especially; the preferred specific gravities, n, is a valid test for the induction of toxicity in the fractions referred, to, and further :is an indication thattoxicity has been inducedin otherfractjijons jofthejmaterhlunderrtreatmentn v v Instead" offemploying benzene, the destructive reforming; of? the" petroleum aromatic may be carried-on in ;.th.e"presence of any. materialjoi ring structure -content" possible of receiving intc :its molecular structurethe cleavage toxicity dilu; Arnong these materials may be mentionedvarious jnaphthenes and'aromatics, as forexample, but not as, a restriction, Y toluo1,j xy lo1,t tr'imethylbenzene, naphT thalene or the 1ike,fand specifically the various naphth'enes capable of receiving into their molecular structure said cleavage diluents.

Example 2.Practice the processor Example ,1 with pelletediBentonite. clay as catalytic material; R

Example 3L-I-PracticeVthe process ofm Example ltwith activated 'attapulgus clay as eatalytic man t'erial.

Example .%Rractice l" the f, process of Example 1 with;ajsilicajhydrogelfiasfcatalytic material. t

n Example; 5. -Practice the. process of Example 1 witha silica hydrogel impregnated with an aluminum saltas catalytic material. 1

Example 6;'-Practicc the process t of 1 Example 1 with bentonite and an adsorptiveiclax.as-catae lytic materials! Examplef'ik Practicefthe process ofEXaniple 1 with a .silicious material impregnated :with metallicoxideas catalytidmateriali v EwdmpleM8.-Pifactice the process (if-Example '1" with a :tsilicious -materials impregnated with a metallic sulfide; as catalyticmaterial. t

EwahipZevQ Pra-ctice the process oft'Example 1 with coprecip'itated alumina and chromia thy;- drogelsias catalytic-materials Example 1.0'.---A furfural extract ,of

toxicity:diluentsrcomprisingz integral parts of ma,

terials i of cyclic structure. lcontent; said cyclic structures having inherent but inhibited toxicity jual r-sludge; if "any," inc-idental to: the blending 01); *eration-"may-be: discarded "if desired: The tolu'ol as stemming from the presence of said diluentsis commin gled with toluol whilstin-a heated condition sufficient to provide a smooth blend. Residrepresents ofthe blend.

perature of.47,0? wlhilstfunder a pressure of tionzofvthe: toxicityedi luents fronr the molecular structure of: the: aromatic" extract f ton-l the r toluol and2(3-) anqoverallrspecific,gravityain-siractional By the-inature of 'the process-=it-is obviousthat mixture or; petroleum fractionsrisaid; extract: boilingxene tirely; between: 26:0 :38.0? Cr, and characterized by I Thevmixtureiofimaterials"is sub jectedjtoa tenrparts of the beneficiated extract falling between thelimits noted in the following tabular data:

Low limit Fractions High limit and preferably between the limits noted below:

Fractions Low limit High limit When processing the furfural extract under the conditions above named, a period of one hour and minutes will illustratively serve to jointly provide (1) the stated newly formed low boiling materials, (2) transference of toxicity diluents as noted and (3 a specific gravity in fractional parts of the beneficiation falling between the preferred stated limits.

When the stated'period of processing has been 'completedQthe, oil is withdrawn from its treating 4 ing point of about 200 C. and about 90% over at.

400 C. is commingled with two parts of benzene. Seven percentof zinc chloride is employed as the catalyst. The mixture and catalyst are charged to a rocking autoclave and heated to a temperature of 210? C. whilst under autogenous pressure for such a length of time as to jointly proenclosure, cooled and inspected. The unreact'ed toluol. if any, and the toluol containing at least a portion of the former toxicity diluents of the aromatic extract are totally or partially removed from the overall beneficiation in any suitable manner, as for example by distillation or the like.

After the total or partial removal of the toluols, the beneficiated furfural extractis found to have enhanced toxic properties as jointly stemming from, among other things, the-formation of the newlycreated low boiling materials and the transference of toxicity diluents to the toluol.

The beneficiated extract of induced toxic properties which has substantial residual matter above 355 C. may be used in toto as a wood preservative or if desired a wood preservative having specification boilingcharacteristics may be segreficiated extract is a valid'test for the induction.

of toxicity in the fractions referred to, and further is an indication that toxicity has been induced in other fractions of the material under treatment.

. Example 11.Practice the process of Example 10 in the presence of a molybdenum oxide catalyst.

Example 12.Pra.ctice the process of Example 10 withmolybdenum and tin oxides as catalytic materials.

Example 13.-Practice the process of Example 10 with chromium oxide as catalytic. material.

Example 14.-Practice the process of Example 10 with vanadium oxide as catalytic material.

Example 15.Practice the process of Example 10 with tin oxide as catalytic material.

Example 16.-Practice' the process of Example 10 with molybdenum sulfide as catalytic material. Example 17.Practice the process of Example 10 with cromium sulfide as catalyticmaterial.

vide (1) newly formed lower boiling fractions of the petroleum above mentioned, (2) transference of toxicity diluents from the molecular structure of the charging stock to the benzene and (3) an overall specific gravity in the materials boiling between 315-355" C. of the beneficiation falling between 0973-11175, and preferably between 1.001-1.1025.

When processing the starting material in accordance with the foregoing disclosure, a period selected between the limits of one and two hours, as for example one and one-half hours, will serve illustratively, to jointly provide (1) the stated newly formed low boiling fractions, (2)

transference of the toxicity diluents from the starting material to the benzene and (3) a specific gravity in the 315355 C. fraction of the beneficiation falling between the preferred stated limits.

' At the end of the processing period, the agitation of the bomb is stopped and the catalyst mass is allowed to settle to the bottom. After the catalyst mass has settled, the overlying layer of oil, without catalyst, is withdrawn and cooled.

The unreacted benzene and the reacted benzene which contain as an integral part at least a portion of the toxicity diluents previously comprising an integral part of the starting material, are partially or totally removed from the beneficiated feed stock in any suitable manner, as for example by distillation. After removal of the said benzene, the beneficiated material may be used in toto as a wood preservative, or a wood preservative of desired boiling range may be segregated therefrom.

The induction and/or provision of the noted specific gravity, and preferably the preferred specific gravity in the materials boiling between 315 C. and 355 C. of the beneficiation is a valid test for the induction of toxicity in the fraction referred to, and further is an indication that toxicity has been induced inother fractions of the material under treatment.

Example 22.Practice the process of Example 21 with aluminum chloride as catalytic material.

Example 23.-Practice the process of Example 21 with potassium chloride as catalytic material.-

Example 24.-Practice the process of Example 21 with ammonium chloride as catalytic material. Example 25.Practi'ce the process of Example 21 with zirconium chloride as catalytic material. Example 26. Pr-actice the process of Example 21 with iron chloride as catalytic material.

Example 27.-Practice the process of Example 21 with manganese chloride as catalytic material.

Example 28.Practice the process of Example 21 with tin chloride as catalytic material.

enclosure andcooled: After removal}.

- .Emampleewr- Practicelthemrocessmt-Example Example 30.- -Practice' the process lof Example.

"2'1withiodoformascatalytic material. 3 Example 31. --Practi-ce the .process; oix'Example n 21 with hydriodic-acid-astcatalyticzmaterial.

Exampleu32 .-n--Practice then-nprocessoiExample 21 with bromine .aslcatalytic material.

said extract havinguan initial boilingpoint rof about 260 .C., substantial residual matter: above 355 C. :and characterized byJ-inherent but in-;

hibited toxicity due qtO the ipresence of wtoxicity 3 diluents is n com m'ingledwwith benzene,vwithtor without additional heatingsasz necessity may? dicminglement. In the eventgsludgeiisrpreeipitated, it may be-discarded if desired. The commingle:

1 isvanuindication.that @toxicityhas :been induced content: having inherent butsinhibited "toxicity tate in order to providearelativelyjsmoothlccmbecausetof thepresence oflsaid diluentsyis comment ,cornprisescfone.=partoof aromatic extnact j and two parts of benzene.

The blended materials are sheated intthenresence of an activated; clay catalyst ata ytemperature of 440 Cwwhilstundena'pressure of 1200 pounds for sucheaa length; of time as to r jointly provide (litransference ostoxicitywdiluen ts from the molecular 1 structure; [of the aromatic extract to the benzene, (2) newly: formed materialss boiling. below235? Cwduei to -the cracking-oi the extract and -(3) -a;speci=fio gravity ofqr naterials of cyclic structure content in lfractional cparts "of i y the beneficiated material iall-ingfbetween the limand preferably betw eirtnf limits oted beib Fractions sLowJimit 1. Highlllmit sis-355C When processingythe aromatic {extractzaccording to the instant: example; a. :periodmf one: hour and l5tminutes-will ill-ustrativeW serve to ,provide-(1) transference xoftoxicity diluentswfrom mercial toxicity, or a preservative wood impregnantrsmay be segregated therefrom complying with :boiling :range. specifications :ex-tantt andAor gravities ofamatenials of cyclic; structure content inriractional; parts. of the beneficiation note'd iin the foregoing is .avalidi test for Lthe inductionvof toxicity in the fractions referred to, and further "Example a35.-.-A furiural; extract of: as mixture of cpetroleum lubricating-fractions; said extract characterized bywtoxicity d-iluents comprisingim tegral parts of: thew-materials ofacyclic structure ation maycbe discarded if desired, \Thatoluol represents; 597% of the, blend. t t y :Theanixture of materials .nis :lsubjected Ito-la temperaturewof 460 ,0. Whilst under a -pressure of-800cpounds-for such;,a;periodi oftime astto jointly provide 1) newly; formed materia1s;;boi;ling: belowj2 35? C. dues to the cracking :of nthetex tract; (2)transferencewof.at least a portionyiof toxicity. diluents 1 from the 1 molecular? structure of-the aromatic extract-ltosthettoluolr and 3) ,a specific gravityv of a materials of cyclic structure content-in fractional; partsoi the "beneficiation 35 y i tabular data:

the molecular structure; ofthearomaticeextract to the benzene, (2) newlyntormed low boiling materials as statedwand- (3);xa specific-ygravity'roi materials of cyclic tstructure A content in r tract-- tionalparts T of the beneficiation falling: between the;preferredtstatedlimits. i i y f When the :processing' speriod :h as :sbeerr t: completed, tl1e-:oi1 is -withdrawndtrom itsitreating part, of; the :unreacted":benzeneaandr theztbenzene 1 formation :roi trnewly created: lowhboilingivmaterials-w and: the transference of. t'cxicityFdiluents to the;benzene. w n r After the par tiefiaor totalvremovaliiof said men.

zenes from t the beneficiated extract which has substantial 'residuat matter above =35 5 Cl.,;r .ithe

b eneficiatedwextractmiaytbei usedin \totovasaa' fallinghbetween the limits noted; inthe vfollowing Fractions and preferably-1.betvveen thelimits noted below uLowlimit W hen processingathe l iuriural extract .in ac! cordance with the instant; example, a. periodmf about onechour williillustratively serve to; jointly provide 1 .thesta-ted low boiling materials,

(2) transference of toxicity odiluentsiasinoted structure content an ,fractionaljlparts gof jjthe beneficiation falling .betweenthe; preferred stated limits. i

Whenlthe stated period of processing hasbeen completed, the oil is-withdrawn-fromits treatit ing enclosure, vcooled ,and. inspected. The ..unreacted toluol, if any, :and thev toluol; containing at least a pcntion of the former toxicity diluents oigthe aromatic extract arectotallyoor partially removed from theuoverall '.beneficiatibn .in any suitable manner, as for example distillation .or

the like.

",After .theg-partial;;,or totalsremovalwof ,the I toluols, the beneficiatedqiurfural; :extract is jointly stemming fromvamong-other: things,nthe formation of?thenewlytcreatedvlbwuboiling materialsand the'transierencenof': toxicity idiluentsfound 'to have enhanced toxicepropertieswas 'Ihevbeneficiatedi extract smaymbeihandledmim preservative wood limpregnantgqhaving comaccordance with the disclosures made in the foregoing.

. The induction and/or provision of the specific gravities of materials of cyclic structure content in fractional parts of the beneficiated material falling between the limits noted in the foregoing is avalid test for the induction of toxicity in the fractions referred to, and further is an indication that toxicity has been induced in other fractions of the material under treatment.

Example 36.-One part of a flashed petroleum residuum having an initial boiling point of about 300 C. and an end point of about 425 C., characterized by induced cyclic structures having toxicity diluents as integral parts of saidcyclic structures is commingled with two parts of benzenel Eight percent of aluminum chloride is employed as catalytic material. The mixture and catalyst are charged to a rocking autoclave and heated to a temperature of 175C. whilst under autogenous presure for such a length of time as to jointly provide (1) newly formedmaterials boiling below 200 C., (2) transference of toxicity diluents from the molecular structure of the charging stock to the benzene and (3) a specific gravity of materials of cyclic structure content in the materials boiling between 3'I5 355 C of the beneficiated material falling between the limits of 1'.027-l.1285, and prefer a v between the limits of 1055-11135.

When employing the process variables disclosed in the instant example, a period of one hour will illustratively serve to jointly provide (1) the statednewly formed low boiling fractions, (2) transference of toxicity diluents from the starting material under treatment to the benzene and (3) a specific gravity of materials of cyclic structurecontent in the fraction 315-355" C. of the beneficiation falling between the preferred stated 'limits.

overlying layer ofoil is withdrawn and cooled.

The unreacted benzene, if any, and the reacted benzene which contains as an integral part at least a portion of the toxicitydiluents previously comprising an integral part of the flashed residuum, are partially or totally removed from the be'neficiated, feed stock in any suitable manner, as for example by distillation. After removal of said benzenes,'the beneficiated feed stock may be used in its overall entirety as a preservative wood impregnant, or a wood preservative impregnant of desired boiling range may be segregated there from in any well known manner, as for example by providing a stabilized residual, a distillate or an extract.

The induction and/or provision of the noted specific gravity of materials of cyclic structure content in the fraction 315-355" C, of the beneficiation is a valid test for the induction of toxicity in the fraction referred to, and further is an indication that toxicity has been induced in other fractions of the material under treatment.

In the instant process various pressures are employable. As for example, but not as a restriction, pressures ranging from a few hundred pounds and upward, and pressures as high as practicable may be employed;

The temperatures of. the instant process when carrying on the operation without a catalyst, or with a catalyst of the silicious type, metallic oxides orsulfides and halogens, halids and derivatives'the'reof, excluding the chlorides, are selected between the limits of about 350-600": CL, and preferably between AGO-500 C. When employing a metallic chloride or the like the temperatures are selected between-70225'C., and preferably between -200 C. Under certain circumstances, various halogens, hali'ds and derivatives thereof, including specificallysubs'titution and addition products thereof, as for example and specifically substitution and-addition products of said derivatives may-be employed at a temperature selected between the limitsbf70-225" C.

The time of treatment will vary according to the'raw material being processed "and the material which is selected to actas' the toxicity diluent recipient. A few trials with any given starting material will enable those skilled in the'art to equal or approximate the objectivesset forth in the foregoing examples. The volume of the-liquid material which acts as the recipient of the-toxicity diluents of the starting material may vary over relatively wide limits, as for example it may represent as little as 25% of the mixture, and may go as high as two;or three times the volume of the starting feed stock Preferably the volume of this liquid isequal' to not less than that of the feed stock, nor more than twice the volume of the feed.

The process of the instant invention may be practiced in an intermittentprocessing vessel or in a continuous-manner as will become apparent to those skilled'in the art afterhaving read the foregoing disclosures. Q

In the examples shown in the foregoing, one or more phases, 'etciof one example'may be added to or substituted for other phase or phases in another example where the substitution or addition is obviously workable.

The evaluation of the-materials of cyclic structure content and/or aromatics referred to inthe.

foregoing and in the annexed claims, is secured by recourse to the. method disclosed under the caption.Ne'utral oils of coal hydrogenationaction of sulfuric acid, Industrial and Engineering Chemistry, Industrial edition, volume 32, page 1614 et seq., December 1940. I

While the various examples disclose the use of definite catalyst with definite controls of the examples, it is to be understood that the catalysts are interchangeable with the definitecontrols of the examples, and any of the namedcatalysts, their equivalents or in combination are usable in any of theexamples. The examples given, and the catalysts linked therewith are for purposes of illustration only. 1

Minorchanges maybe madewithin the scope of the appended claims without departing from the spirit ofthe invention. In the claims affixed to this specification no selection of any particular modification isintended to the exclusion of other modifications. thereof, and the right to subsequently make claims to any modification not cov ered by these claims is expressly reserved.

We claim:

1. The process of inducing toxicity into a relatively high boiling mixture of petroleum fractions characterized by a substantial percentage of materials ,of cyclic. structure content, said cyclic structures having inhibited toxicity due to toxicity' diluents which appear as integral parts thereof, which comprises: contacting said relatively'high' boiling .mixture of petroleum fractions with a relatively low boiling oilof cyclic content adapted to receive as an integral part thereof at least a. portion of said toxicity diluents of i said mixture rendering the mixture: of

' 1 petroleum fractions moretoxic by :heat. treating the contacted materials at a .temperature-lse lected between the limits of about'350600C. whilst under superatmospheric pressure fora period not in excessof -abouttwo hours, said period "beingyso selectedwith reference to thewchosen temperature and pressure'as to jointlyqiprovide newly formed low boiling materials in' saidmixture of petroleum fractions, transference (of at least a portion of said toxicity diluentsfrom the 1 mixture of petroleum fractions to saidirelatively low boilingmoil of cycliccontent; a; specificgravity in fractional :parts of l the; heat treated mixture and recovering from "the heat treated contacted materials at least a portion ofthe reacted and unreacted relatively low boiling materials of cyclic 'mainder thereof as material of induced some ma am properties; and segnegatingfroin thebeneflciated materialan oil of thewood preservativetype boile i eprep erantlrbetwe n andI355 C-rsaid oil characterized by inducedtoxic properties and end point at least as high asabout355 Q. :and substantial. residual material 1 boiling above 31.5? (1., the fractions 270-3315-C.-and- 3-15-355 C; of

. which have specific -gravities falling between the limits above named.

l 3. The: process .of inducing toxicityYin-to-arel atively high boiling mixture of petroleum fractions characterized by asubstantial percentage of materials ofcyclic structurecontent, said cy- 3 1 0110 structures havinginhibited toxicity dueto 15 toxicity diluentswhich appear as integral parts thereof, which comprises: contacting said relatively high boiling mixture of petroleum fractions withra relativelylow; boiling oilof cyclic content adapted to receive ast anintegral part their-69f at least.aqportioni of gsaid toxicity idiluents of said -mixture; rendering the :mixture f petroleum :fractions more toxic by heat treating the contactedmaterials in the. presence of a mestructure content whereby to provide" the reproperties; and segregating from thebenef ciated material an oil of the wood preservative *type boiling preponderantly between 210 C, and 355 C.,said oilicharacterizedl by inducedtoxicprope erties,andend point at least as high as about 355 C. and substantial residual material'boiling above 315 CL, the fractions 235-270 C., 270- 1 grayities falling between the limits aboveTnamed.

2. The. processof inducing toxicity into a'irelatively high boiling mixture of petroleum fractions characterized by .a substantial percentage of materials of cyclic structure .content saidcy- 9011 structures having inhibited toxicitydue t said mixture of petroleum fractions, transference 1 toxicity diluents which appear as integral parts thereof, which comprises: contacting s'aidrelatively'liigh boiling mixture of petroleum fractions with a relatively low boiling oil of cyclic contentadapted \to receive as an integralhpart thereof at leastfa portion of said toxicity diluents of said mixture; rendering the mixtureof petroleum fractions moretoxi-c by heat treating the contacted materials at a temperature selected between the limits of. about 350-600 C. whilst under superatmospheric pressure for a periodnojt in excess of about two hours, said periodbeing sotselected with reference to thechosentemper'ature and .pressure as toiointly provide newofpetroleurn fractions, transference ofat least a portion of said toxicitydiluents' from the mixlyforined low boiling materials in said mixture ture of petroleum fractions to said relatively low 1 boiling ,oiljof Cyclic. content, a specific rav ty in fractional parts of .theheat treated mixture of petroleuin"fractionsffallingbetween the following limits: i

raction to m t ni t and recovering fromtheheat treatedcontacted 1 1 materials atleastaportionofthe:reacted and unreacted relatively lowboilingmaterials of cyclic structure content. whereby. to .providemthe remainderathereof;asmaterial of induced toxic {Iii Q. whilst under superat o h gm; 1

the followinglimits: 1

tallic chloride as catalytic agent, at Ka -tempera..-

ture selected, between; the alimits of about; 70 225? Y 6.. Whilst under superatmosphericl pressure for a period not in excess of -about-two hours, said period bein g-s01se1eeted with reference tp the chosen temperature and pressu re as lto'join tly provide newly formed low boilingmaterials ;-in

of at least a portion of saidtoxicity diluents from the mixture of petroleum fractions tot said relatively low 1 boiling; oi1of cyclic content, a; specific gravity in fractional parts "of the heat treated mixture of petroleum fractions falling between Fractions "Lowlimit 1 "Highlimit res-270 0. 850: 1.0315 270T315 o 0.914 1-. 0691 and recoveringQfrom the contactedheattreated materials at. least Zaportion ofthe reacted and ilnreacted. relatively'jlowboiling materials of cyclic structure content whereby to provide the remainder 3 thereof material of induced toxic properties; and segregating from the beneficiated material anoil of the wood preservative type boiling preponderantly between 210. C. and 355 C., said oil characterized by induced toxicqpr'operties; and end point at least ashigh asabout 355 C. and substantial "residual material boil- 1 ing above 315C; the fractions235 270 C.;270-

315 C. and 315-355" C. of which have specific gravities falling between the limits above named.

4. The process ofinducing "toxicity into a relatively high boiling mixture of petroleum fractions characterized by a substantial percentage of materials of cyclic structure-content, said cyclic structures having inhibited toxicitytdue to toxicity diluents which appear as integralparts thereof, which comprises: contacting said relatively high boiling mixture of petroleum fractions witha relatively low boiling oil of cyclic content 1 adapted to receive as an integral part thereof at;least'a portion of said ,toxicitydiluents of said mixture; renderinglthe mixtur of petroleum fractions more toxic by heat-treating Fractions Low limit High limit 270315 C 0.914 1.0691 3l5355 C Q 0.973 1. 1175 and recovering from the heat treated contacted materials at least a portion of the reacted and unreacted relatively low boiling materials of cyclic structure content whereby to provide the remainder thereof as material of induced toxic 7 properties; and segregating from the beneficiated material an oil of the wood preservative type boiling preponderantly between 210 C. and 355 C., said oil characterize-d by induced toxic properties, and end point at least as high as about 355 C. and substantialresidual material boiling andsubstantial residual material boiling above 315 C.,, the fraction 235270 C., 2'70315 C. and 315-355 -C. of which contain materials of cyclic structure content having specific gravities falling between the limits noted above. 7

6. The process of inducing toxicity into a rela-v tively high boiling mixture of petroleum fractions characterized by a substantial percentage of materials of cyclic structure content, said cyclic structureshaving inhibited toxicity due to to'xicity diluents which appear as integral parts thereof, which comprises: contacting said relatively highboiling mixture of petroleum fractions with a relativelylow boiling oil of cyclic content adapted to receive as an integral part thereof at least a portion of said toxicity diluents of said mixture; rendering the mixture of petroleum fractions more toxic by heat treating the contacted materials at a temperature selected between the limits of about 350600 C. Whilst under superatmospheric pressure for a period not in excess of about two hours, said period being so selected with reference to the chosen temperature and pressure as to jointly provide newly'formed low boiling materials in said mixture of petroleum fractions, transference of at least a portion above315 C., the fractions 2.70315 C. and 315- 355 C. of which have specific gravities falling between the limits above named.

5. The process of inducing toxicity into a relatively high boiling mixture of petroleum fractions characterized by a substantial percentage of materials, of cyclic structure content, said cyclic structures having inhibited toxicity due to toxicity diluents which appear as integral parts thereof, which comprises: contacting said rela-' tively. high boiling mixture of petroleum fractions with a relatively low boiling oil of-cyclic'content adapted to receive as an integral part thereof at least a portion of said toxicity diluents of said mixture; rendering the mixture 'of petroleum fractions more toxic by heat treating the contacted materials at a temperature selected between the limits of about 350-600" C. whilst under superatmospheric pressure for a period not in excess of about two hours, said period being so selected with reference to the chosen temperature and pressure as to jointl provide newly formed low boiling materials in said mixture of petroleum fractions; transference of at least a portion of said toxicity diluents from the mixture of petroleum fractions to said relatively low boiling oil of cyclic content, a specific gravity of materials of cyclic structure content in fractional parts of the heat treated mixture of petroleum fractions falling between the following limits:

Low limit Fractions High limit ass-270 o 0. 935 1. 0756 270-315 O.- 0.973 1. 093a 3154,55 C 1. 027 1.1285

remainder thereof as a material of induced toxic properties; and segregating from the beneficiated material an oil of the wood preservative type boiling preponderantly between 210 C. and 355 C., said oil characterized by induced toxic properties,

and end point at least ashigh as about 355 C.

of said toxicity diluents from the mixture of petroleum fractions to said relativelylow boiling oil of cyclic content, a specific gravity of materials "of cyclic structure content in fractionalparts of the heat treated mixture of petroleum frac- }tions falling between the following'limits:

Fractions Low limit High limit 270-315 C c973 1.0933 315F355 c; 1; 027 1.1285

and recovering from the heat treated contacted materials at least a portion of the reacted and unreacted relatively low boiling materials of cyclic structure content whereby. to provide the remainder thereof as a material of induced toxic properties; and segregating from the beneficiated material an oil of the wood preservative typeboiling preponderantly between 210 C. and 355 C.', said oil characterized by induced toxic'properties, and end point at leastas high as about 355 C. and substantial residual material boiling above 315 C., the fractions 270-315 C. and 315-3550.

of which contain materials of cyclic structure con- .tent having specific gravities falling between the limits noted above.

7. The process of inducing toxicity into a relatively high boiling mixture of petroleum fractions characterized by a substantial percentage. of materials of cyclic structure content, said cyclic structures having inhibited toxicity due-to toxicity diluents which appearas integral parts thereof, which comprises: contacting said relatively high boiling mixture of petroleum fractions with a relatively low boiling oil of cyclic chosen temperature and pressure as to jointly provide newly formed low boiling materials in said mixture of petroleum fractions, transference of at least a portion of said toxicitydiluents from the mixture of petroleum fractions to said relatively low boiling oil of cyclic content; a specific gravity of materials of cyclic structure content in fractional parts of the heat treated mixture of petroleum fractions falling between the following limits:

Fractions Low limit High limit and recovering from the heat treated contacted materials at least a portion of the reacted and remainder thereof as a material of induced toxic properties; and segregatingfrom thebeneficiated material an oil of the wood preservative type boiling preponderantly between 210 C. and 355 C., said oil characterized by induced toxic properties, and end point at least as high as about 355? C. and substantial residual materialboiling .above 315 0., the fractions 235-270 (2., 270 315 C. and 315-35550. of which contain materials of provide newly formed low boiling materials in saidmixture of petroleum fractions, transference of at least a portion of said toxicity diluents from ,unreacted relatively low boiling materials of cyclic structure content whereby to provide the cyclic structure content having specific gravities falling between the limits noted above.

8. The process of inducing toxicityinto a relatively high boiling mixture of petroleum fractions characterized by a substantial percentage of materials of cyclic structure content, said cyclic structures having inhibited toxicity due to tox icity diluents which appear as integral parts thereof, which comprises contactingsaid relatively highgboiling mixture of petroleum fracthe mixture of petroleum fractions to said relatively low boiling oilfof cyclic content, a specific gravityof'materials of cyclic structure content in fractional parts of the heat treated mixture of petroleum fractions falling between theyfollowing limits:

Fractions 1 Low limit High limit 2703l5 C; 0.973 1.0933 315-355 O a 1. 027 1. 1285 and recovering from the heat treated" contacted materials at leasta portion of the reacted and unreacted relatively low boiling materials of cyclic structure content whereby fto provide the remainder thereof as a material of induced toxic properties; and segregating from the beneficiated material an oil of the wood preservative type boiling preponderantly between 210 C. and 355 C.,

tions with a relatively low boiling oil of cyclic content adapted toreceive as an integral part thereof at least a portion of said toxicity diluents of said mixtures rendering the mixture of pcsaid oil characterized by induced toxic properties,

and endpoint at least as high as about 355 C.

and substantial residual material boiling above 315 C., the fractions 270-315 C. and 315-355 C.

- of which contain materialsof cyclic structure falling between content having specific gravities the limits noted above. i

JACQUELIN E. HARVEY, JR.

ROBERT WHITE, JR. JOSEPH A. VAUGHAN. 

